KR100365104B1 - Method for preparing functional polymer via enamine of acetoacetate and polymer produced thereby - Google Patents

Abstract

The present invention relates to the preparation of polymers having reactive functional groups.

More specifically, the present invention relates to preparing a polymer containing a functional acetoacetate group and then reacting the acetoacetate group with a functional amine to form an enamine.

The polymers of the present invention are used in a variety of applications, including coatings, sealants, adhesives and saturators and are most useful as solutions or dispersions in water or water-co-solvent mixtures.

Description

Process for preparing functional polymer via enamine of acetoacetate and polymer produced thereby

The present invention relates to the preparation of polymers having reactive actuators. More specifically, the present invention relates to preparing a polymer containing a functional acetoacetate group and then reacting the acetoacetate group with a functional amine to form an enamine.

The polymer of the present invention is used in various fields such as coatings, sealants, adhesives and saturators, and is useful as a solution or dispersion with water or a water-cosolvent mixture.

Coatings prepared from the composites of the present invention exhibit improved properties such as solvent resistance, dust adsorption, print and block resistance, defect resistance, adhesion and impact resistance and tensile strength such as tensile strength.

In general, it is known to be useful to modify the properties of a polymer by incorporating one or another necessary functional group into the polymer molecule.

The required functional groups can be incorporated either as monomers during polymer preparation or as compounds already having such functional groups, or by converting the polymers with precursor groups to the required functional groups by post-reaction with the appropriate reagents.

The inventors have discovered a new, unexpected and useful method of post-reacting a polymer with precursor groups to incorporate the necessary functional groups into the polymer.

An advantage of the present invention is to provide a process in which the functional polymer is prepared by post-polymerization.

Another advantage of the present invention is that new monomers having functional groups are provided.

The present invention has the additional advantage of providing a polymer having functional groups that are not miscible during the polymerization process.

It is generally known to incorporate the necessary functional groups to control the properties of the polymers, but related art has been disclosed for the preparation of polymers containing functional acetoacetate groups and the formation of enamines by post-polymerization of acetoacetate groups and functional amines. Is not.

European Patent Patent EP. 0 442 653 A2 is a polymer having a carbon or nitrogen-bound-NH ₂ and / or -NH ₂ -precursor group capable of reacting with an enolic carboxyl group with one enol carboxyl group and at least one Y. Disclosed is a method for preparing a polymer having a required Y by reacting at least one compound, wherein an enol-type carboxyl group is a carboxyl group having enol-type properties by being bound to an α -methylene or methane group attached to a group for recovering electrons. it means.

European patent application EF 0 483 583 A2 discloses the reaction of polyacetoacetate or polyacetoacetamide with an alkoxy-silane containing an amino group to prolong the process time and obtain a polyenamine that crosslinks without the effect of atmospheric humidity. .

This is advantageous for films having a thickness of 50 μ or more.

Hereinafter, the present invention will be described.

In one aspect of the invention, the acetoacetate functional polymer is reacted with a compound having an amine group and at least one additional functional group to produce a polymer having additional functional groups attached by the enamine of the acetoacetate group. .

In another aspect of the invention, the acetoacetate functional monomer is reacted with a compound having an amine group and at least one additional functional group to produce a new functional monomer. This monomer can then be polymerized to form a functionalized polymer.

In another aspect of the present invention, a polymer prepared by polymerizing an acetoacetate functional monomer is reacted with a compound having an amine functional group and at least one immiscible functional group that cannot maintain functional activity under polymerization process conditions.

The enamine of the acetoacetate group results in a new polymer having immiscible functional groups attached to the polymer.

In still another aspect of the present invention, a polymer functionalized package and functionalization method are provided. Acetoacetate functional polymer backbones can be prepared, and the ratio of the compounds having amine groups and at least one additional functional group is determined in one molar excess of amine based on acetoacetate to meet the specific properties required for end use. Less than one mole can be changed in excess.

This makes it possible to maintain the inventory as a relatively small type of polymerisation product and to vary the end use of the polymer by selecting the amount of amine reactant to functionalize the polymer.

According to another aspect of the present invention, a method is provided for allowing the required functional groups to be concentrated in the required area, for example the surface of the polymer particles.

The polymers of the invention having functional groups attached through the enamines of acetoacetate groups are useful in coatings, adhesives, polymer mixtures, plastic additives, dispersants, tangles and separation techniques.

polymer

Preferred polymers used in the present invention are vinyl polymers which optionally have pendant acetoacetate groups known as β -ketoesters. As used herein, the term "pendant" means "attached to the polymer backbone and available for subsequent reactions." Pendant is not a strict meaning that excludes the attachment of such groups to the ends of the polymer chains. Thus, polymers having acetoacetate functionality introduced at the chain ends by acetoacetate functional mercaptans, as taught in US Pat. No. 4,960,924, are useful in the present invention.

Generally, pendant acetoacetate groups are attached to the polymer skeleton via organic divalent radicals R ¹ attached to the acetoacetate moiety or trivalent organic radicals R ² having two acetoacetate groups.

Acetoacetate functional polymers can be prepared by means known in the art. Polymerization by incorporation comprising an acetoacetate functional monomer is a preferred method. Hereinafter, acetoacetoxyethyl methacrylate represented by AAEM in this specification is a preferable monomer.

Other monomers useful for introducing acetoacetate functionality include acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, allylacetoacetate, acetoacetoxybutyl methacrylate. There is such a thing as 2,3_di (acetoacetoxy) propyl methacrylate. In general, any polymerizable hydroxy functional monomer can be converted to the corresponding acetoacetate by reaction with diketene or other suitable acetoacetylating agent (eg, Comparision of Methods for the Preparation of Acetoacetylated). Coating Resins, Witzeman, JS; Dell Nottingham, W .; Del Rector, FJ Coatings Technology; Vol. 62, 1990, 101.)

Vinyl polymers of the present invention are the most common copolymers of acetoacetate functional monomers and other monomers. Examples of useful comonomers include ethylene, simple olefins such as alkyl acrylates and methacrylates having 1 to 20 (more preferably 1 to 8) carbon atoms in the alkyl group, vinyl acetate, acrylic acid, methacrylic acid, acryl Nitrile, styrene, isobornyl methacrylate, acrylamide, hydroxyethyl acrylate and methacrylate, hydroxypropyl methacrylate and acrylate, N-vinyl pyrrolidinone, butadiene, isoprene, vinyl chloride and vinylidene chloride Such as vinyl halides, alkyl maleates, alkyl fumarates, fumaric acid, maleic acid and itaconic acids. It is also possible and sometimes desirable to incorporate controlled amounts of gels into the latex particles by containing minor levels of divinyl or polyvinyl monomers such as glycol polyacrylate, allyl methacrylate, divinyl benzene. However, it is important at this time that the quality of the film formation is not significantly impaired.

In addition, chain transfer agents may be included to control the molecular weight of the polymer.

The acetoacetate functional polymer may contain about 0.5-100% by weight of acetoacetate functional monomer. In any application, the amount of acetoacetate functional monomer required will vary depending on the degree of postfunctionalization required for the particular end use application. In general, however, the concentration of acetoacetate monomer is 1-40%. Conventional coatings generally contain about 0.5-20% by weight of acetoacetate monomers. Polymers having a molecular weight of 1,000 to 1,000,000 or more can be used. Low molecular weight polymers should contain sufficiently high levels of acetoacetate to maximize the degree of post-functionalization.

For example. AAEM copolymers having a molecular weight of less than 10,000 typically contain at least 30% AAEM.

Generally, such vinyl polymers are prepared from dispersions or emulsion polymers in water by appropriate free radical initiation polymerization methods using a free radical initiator and heating appropriately. Since film forming polymers are sometimes required, useful emulsion polymers generally have a glass transition temperature of less than 60 ° C. because they form a good film at ambient temperature with the binder.

If soluble polymers are used in the film forming process, polymers with higher glass transition temperatures are readily used by forming films.

In a particular aspect of the present invention, polymerization in aqueous media, and especially aqueous emulsion polymerization, are used for the preparation of polymers. Conventional dispersants may be used (eg, anionic and / or nonionic emulsifiers such as alkali or ammonium alkyl sulfates, alkyl sulfonic acids, and fatty acids, oxyethylated alkylphenols). The amount of the dispersant used is generally 0.1 to 6% by weight based on the total monomer weight. Thermal or redox initiation processes may be used. Conventional free radical initiators (hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, organic hydroperoxides such as ammonium and / or alkali persulfate, t-butyl perpivalate, t- Organic peroxides such as butyl perbenzoate, benzoyl peroxide, di (n-propyl) peroxydicarbonate, acetyl cyclo-hexylsulfonyl peroxide) may typically be used at 0.05-3.0% by weight based on the total monomer weight . Redox systems (e.g., reducing sugars such as isoascorbic acid, sodium bisulfite, sodium thiosulfate, hydroxyl amines, hydrazines, sodium hydrosulfite) using the same initiator combined with a suitable reducing agent are often examples. For example, it can be used at a similar level with metal catalysts such as transition metal salts such as iron sulfate, copper sulfate and vanadium sulfate. Additionally, 2,2'-azo-bis-isobutyronitrile, 4,4'-azo-bis (4-cyanopentanoic acid), 2,2'-azo-bis (2-amidinopropane) Non-oxidative thermal initiators such as dihydrochloride can be used. Often a chain transfer agent such as mercaptan (e.g., 0.05-6% by weight of n-octyl mercaptan, n-dodecyl mercaptan, butyl or methyl mercaptopropionate, mercaptopropionic acid, based on the total weight of monomers) ) To adjust the molecular weight.

The present invention may also be practiced using solvent-soluble or water soluble polymers.

If this is necessary, the polymer can be prepared directly from water if the monomer mixture is water soluble or if the polymerization solvent is a solvent miscible with water, such as isopropanol, butyl cellosolve, propylene glycol, etc., as is often the case. have. In such a case, water may be included in the polymerization mixture or post-added after completion of the polymerization. In some cases, the polymer may be prepared in conventional organic solvents such as xylene, butyl acetate, methyl ethyl ketone, methyl tert-butyl ether. If an organic solvent is used alone or in combination with water, it is convenient and smooth to copolymerize organic soluble-free radical initiators such as azo-bis-isobutyronitrile, t-butyl-peroctoate or benzoyl peroxide. It is convenient to heat Another method of preparing the water soluble polymer of the present invention is a vinyl dispersion having an amount of acrylic or methacrylic acid or other polymerizable acid monomer (generally 10% or more) such that the emulsion polymer is solubilized by addition of ammonia or other bases. To prepare a polymer. Water soluble polymers of this type are usefully used as mixtures with conventional dispersion polymers, preferably those which also have pendant acetoacetate functionality. Mixtures of alkali-soluble resins and latex polymers have particularly useful properties that combine gloss and rheology properties and are useful for coatings and printing inks.

In another aspect of the invention, the aqueous dispersion contains copolymer particles composed of at least two mutually incompatible copolymers. These non-miscible copolymers may be present in morphological arrangements such as core / shell, core / shell particles with incomplete shell phase surrounding the core, core / shell particles with multiple cores, permeable reticulated particles. . In all such cases, most particle surfaces will be occupied by at least one outer phase and the interior of the particles will be occupied by at least one inner phase. Non-miscible properties of the two polymers can be measured by various methods known in the art. For example, using a scanning electron microscope using a coloring technique to highlight the difference in appearance of these phases is one such technique.

Emulsion polymerization techniques used to prepare such dispersions are well known in the art. Low levels of allyl methacrylate, diallyl phthalate, diallyl malate, butylene glycol dimethacrylate, divinyl benzene, triallyl isocyanurate, ethylene glycol diacrylate in the core through It is sometimes advantageous to introduce some crosslinking or gel structures in a continuous polymerization process. Slightly cross-linked cores do not adversely affect encapsulation and in some cases make the coating better, especially when pendant acetoacetate is concentrated in the shell.

As noted above, the primary use for this technique is to functionalize vinyl polymers dispersed or dissolved in aqueous solvents. Unfortunately, vinyl polymers containing pendant acetoacetates are susceptible to hydrolysis, especially in water aging. Hydrolysis at almost all pH yields acetoacetic acid, which is then broken down into acetone and carbon dioxide.

USSN 632,302 solved this problem by treating an aqueous aceto acetate polymer with one molar equivalent of ammonia or a primary amine such as ethanolamine, methyl amine, or isopropyl amine. As described in the above application, the polymer is typically neutralized with a basic pH, preferably with a pH of at least 9, with one of the amines described above. Under this condition, an enamine is produced. Enamine formation reactions generally generate faster as the temperature increases. In general, enamine production is completed within 8 hours. An alternative method of increasing the pH to about 9 is to equilibrate the system and adjust the pH back to about 9 to replace the amine consumed by the enamine production. Enamines are typically stable against hydrolysis when the pH is above 7.

We have found that the enamine reaction pathway provides a method for attaching additional functional groups or functionalized chains to the acetoacetate polymer. In the following formula, R ² represents a functional group or a linking group having a functional group.

Three-dimensional hindered primary amines such as t-butyl amine and aromatic amines such as aniline are generally less suitable because of the incomplete formation of enamines. Because enamine formation is a reversible reaction, the amine compound must be nonvolatile if the functional group is exposed to the atmosphere before it is used. However, the wet composition has good storage stability as long as it is stored under conditions (such as a closed container) where volatile amines do not evaporate.

Another method of preparing vinyl polymers containing the same amount of pendant enamine functionality is to use preformed enamine monomers derived from suitable amine and acetoacetate monomers. In this case, the pH should be kept alkaline in order to prevent the enamine from hydrolyzing to acetoacetate during polymerization.

Functional group

In formula -R ² NH ₂ , R ² can be a functional group or a bonding group having a functional group. Examples of the bonding group include _divalent groups such as C ₂ -C ₁₈ alkyl, alkoxyl and polyalkoxy such as polyoxyethylene and polyoxypropylene having a molecular weight of 72-400,000. Examples of the property-imparting functional groups that can be attached by the method of the present invention include a cross linking group, an adhesion promoter, an ultraviolet blocker, a surface active compound, a latex stabilizer, and a separating bonder. For example, mercaptoethyl amine, taurine, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, polyoxypropyleneamine, polyoxyethyleneamine, 2-aminoethylethyleneurea, 2-dimethylamino Functional groups in the form of ethylamine, amino acids, alkylamines, 4-amino-2,2,6,6-tetramethylpiperidinyloxy-free radicals are well known in the art.

In one embodiment, compounds having amine functionality and additional functional groups have both primary and secondary or tertiary amine functionality for enamine production. In the case of tertiary amines, a route to cationic latex is provided; When the tertiary amine functional polymer is treated with a proton source or an alkylating agent, ammonium cations can be produced.

For example, the steric stabilized latex may be produced by the reaction of an acetoacetate polymer with a polyethoxylated amine. This method also provides a way to control the polarity of the polymer by selecting from hydrophilic or hydrophobic amines. Likewise, the refractive index of the polymer can be controlled by increasing or decreasing the refractive index using appropriate functional groups for the amine. By adding functional groups selected for one or two polymers, the miscibility of the various polymer pairs upon mixing can also be improved.

Monomers having certain functional groups are generally not suitable for incorporation into polymers because the functionality can be changed chemically under polymerization conditions or the functional groups can have undesirable effects on the polymerization process. For example, mercaptan functional groups cause chain transfer effects during free radical polymerization, resulting in a lower molecular weight of the product than when functional groups without chain transfer effects are used.

The olefin functional group is consumed in the free radical polymerization process but can be added later according to the invention. Secondary amines can cause reaction delays and chain transfer during free radical polymerization.

additive

The polymers and additives of the present invention may be combined for the selected end use. Additives such as thickeners, dispersants, pigments, weightants, fillers, antifreezes, plasticizers, adhesion promoters, binders, wetting agents, antifoams, colorants, non-aldehyde based insecticides, soaps and slip agents may be incorporated. have.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described.

Unless stated otherwise, percentages are parts by weight based on total solids.

Example 1

Ammonium salt of water 501,7gr, Rhodapex CO-436 (sulfurized nonylphenoxypoly (ethyleneoxy) ethanol: ) Polymers were prepared from monomer mixtures containing 18.1 gr, methacrylic acid 7.5 gr, acetoacetoxyethyl methacrylate 597.6 gr, methyl methacrylate 888.9 gr and n-dodecyl mercaptan 44.9 gr. 47.2 gr were taken from this monomer emulsion mixture and added to a vessel containing a mixture of 1317.9 gr of water heated to 85 ° C. and 8.74 gr of Rhodapex CO-436. An initiator charge with 2.26 gr of sodium persulfate was added to 50.0 gr of water. After 10 minutes, the residual monomer emulsion began to be added slowly over 2 hours in an independent feed with 1.13 gr of sodium persulfate dissolved in 157 gr of water. After 2 hours, the emulsion was cooled to ambient temperature.

Solubilization of polymers

To 500 g of an emulsion having reduced solids to 41.8% with water was added 370 gr (0.95 equivalents based on acetoacetate functional group) of a primary amine terminated polyethoxylate (Jeffamine M-1000, Texaco) of 1000. The resulting mixture became a clear solution with a highly viscous material (Brookfield viscosity 7160 cps) with the same rheology as the solution.

This example shows that the emulsion polymer can be solubilized with a suitable amine to form a uniform solution resin by enamine formation.

Example 2

501.7 gr of water, 45.7 gr of sodium dodecyl benzene sulfonate solution, 19.42 gr of methacrylic acid, 298.8 gr of acetoacetoxyethyl methacrylate, 578.2 gr of methyl methacrylate, 597.6 gr of butyl acrylate and n-dodecyl mer The polymer was prepared from a monomer mixture containing captan 3.0 gr. 47.2 gr were taken from this monomer emulsion mixture and added to a vessel containing a mixture of 1317.9 gr of water heated to 85 ° C. and 22.0 gr of sodium dodecyl benzene sulfonate solution. An initiator charge was added which dissolved 2.26 gr of sodium persulfate in 50.0 gr of water. After 10 minutes, the residual monomer emulsion was slowly added over 2 hours in an independent feed with 1.13 gr of sodium persulfate dissolved in 50 gr of water. After 2 hours, the emulsion was cooled to ambient temperature. To the aliquot of the emulsion was added one equivalent of the amines shown in Table A below. The latex polymer was equilibrated for 2 days prior to lyophilization and the Tg of the polymer was measured by differential scanning calorimetry.

Table A- Effect of Enamine Formation on Tg of Polymers

This example illustrates that the Tg of the polymer can be controlled by post addition of selected primary amines after polymer production to form the corresponding enamines.

Example 3

Functional monomer 1 (ethylethyleneureaeneamine of allyl acetoacetate)

Allyl acetoacetate (77 gr, 0.543 moles) was treated with aminoethylethyleneurea (70 gr, 0.543 moles) in 149 gr of ethyl acetate containing 0.4 gr of phenothiazine to prepare a functionalized monomer. The reaction mixture was heated to reflux for a total of 13 hours in connection with a Dean-Stark trap (used to remove water azeotropically). Thereafter, the reaction solvent was removed using a rotary evaporator under reduced pressure to yield a total of 122 gr of product.

Example 4

Functional monomer 2 (hydroxyethylenamine of AAFM)

Functionalized monomers were prepared by treating acetoacetoxyethylmethacrylate (AAEM) (200 gr) with ethanolamine (62.7 gr) in 500 gr of methylene chloride. The reaction mixture was stirred at room temperature for 20 minutes, heated to reflux for 1 hour, and then cooled to room temperature. The cooled reaction mixture was poured into a separatory funnel and washed twice with saturated sodium chloride solution. The organic solution was then dried using anhydrous potassium carbonate. The dried organic solution was filtered to remove potassium carbonate. The resulting organic solution was then concentrated under reduced pressure using a retroevaporator to yield the required product 239 gr: 1 H NMR (270 MHz, CDCL3) d 1.85 (br s, 6H), 3.3 (br q, 2H), 3.62 (br t, 2H), 3.8 (m, 1H), 4.2 (m, 4H), 4.38 (s, 1H), 6.02 (s, 1H), 8.5 (m, 1H).

Example 5

Preparation of Solution Polymers Using Enamine Functionalized Monomers

The reaction flask containing 286 gr of xylene was heated to 105 ° C. under a nitrogen atmosphere. With a t-butylperoctoate 6gr mixture in which 14 g of butyl methacrylate, 67 g of butyl acrylate, 10 g of enamine formed from AAEM and ethanol amine in Example 4, and 3 g of methacrylic acid were dissolved in 14 g of xylene. At the same time it was fed to the reaction vessel over 2 hours. The reaction was then held at 105 ° C. for an additional 30 minutes, at which time 0.5 gr of t-butylperoctoate was added to the reaction mixture. The reaction was maintained at 105 ° C. for 10 minutes and then cooled to room temperature. Samples were dried in an oven at elevated temperature (150 ° C. for 30 minutes) and the final solution was a polymer with 38% by weight solids. The UV spectrum of the polymer thin film cast on the quartz disk indicates that the polymer contains an enamine structure. The UV spectrum showed a large absorption characteristic of β -aminocrotonate at a wavelength of 283 nm.

Example 6

Vinyl acetate emulsion polymer

Water (heated to 60 ° C.) 1026 gr, 45% solution containing 100 nm BA / MMA / MAA latex polymer 60gr, sodium persulfate 2.75% aqueous solution 24gr, sodium bisulfite 1.25% aqueous solution 24gr, ferros sulfate 0.2 % Reaction solution containing 12.0 gr of aqueous solution, 3 gr of acetic acid and 3 gr of sodium acetate, 490 gr of water, 58% ammonium salt solution of nonylphenoxypolyethylene oxide sulfonate (Rhodapex CO-436) 1.8 gr, 3 gr of acetic acid, 3.6 g of sodium acetate, A monomer mixture containing vinyl acetate 2083.4 gr, sodium vinylsulfonate 21.6 gr and allyl acetoacetate 71.3 gr was added to prepare an emulsion polymer having a total composition of vinyl acetate 96.45 / allylacetoacetate 3.3 / sodium vinylsulfonate 0.25. The monomer emulsion was fed to a reaction vessel over 3.5 hours under nitrogen atmosphere simultaneously with a solution of 120 gr of 2.25% sodium bisulfite solution and 2.4 gr of t-butylhydroperoxide, 1.8 gr of sodium persulfate and 120 gr of water. After the monomer was added, the reaction was kept at 60 ° C. for 15 minutes, and then a 30 gr solution of an aqueous 8% t-butylhydroperoxide solution was added to the vessel along with 120 gr of an aqueous 5% isoascorbic acid solution. The reaction was then cooled to room temperature yielding a latex containing 51.6% polymer solids.

Example 7

Functionalization of Vinyl Acetate Emulsion

100 gr of the emulsion polymer sample of Example 6 was treated with 1.55 gr of aminoethylethyleneurea. The reaction was kept at room temperature. The next morning, the polymer thin film on the quartz disk was found to have UV absorption peak characteristics of the β -aminocrotonate structure of wavelength 280 nm.

Example 8

(Meth) acrylate emulsion polymer

From a monomer mixture containing 629.99 gr water, 9.89 gr sodium 23% aqueous dodecylbenzene sulfonate, 790.02 gr butyl acrylate, 686.57 gr methyl methacrylate, 376.20 gr acetoacetoxyethyl methacrylate and 28.22 gr methacrylic acid The polymer was prepared. From 58.72 gr of this monomer emulsion were added to a reaction vessel heated to 85 ° C. containing 1577.93 gr of water, 8.22 gr of sodium dodecylbenzene sulfonate aqueous solution, 8.22 gr of sodium persulfate 3.02 gr. The monomer emulsion was added to the vessel simultaneously with 50 gr of 1.7% aqueous solution of sodium persulfate over 180 minutes. After addition, the reaction was held at 85 ° C. for 30 minutes and then cooled to 65 ° C. When the reaction mixture reached 65 ° C, 1.04% ferrous sulfate 0.48% aqueous solution, 0.54gr 70% active t-butylhydroperoxide dissolved in 19gr water and 0.38gr isoascorbic acid dissolved in 19gr water It was added to the reaction vessel. The reaction was held at 65 ° C. for 15 minutes and then cooled to room temperature. An emulsion polymer with 43.3% solids was produced.

Example 9

Preparation of Cationic Latex

10 gr of the latex sample prepared in Example 8 was diluted with 33.3 gr of 0.1 M potassium potassium chloride and 0.18 gr of Triton X-405 (70% aqueous solution, Union Carbide). The latex was then treated with 0.356 gr of dimethylaminoethylamine and equilibrated overnight. Acoustophoretic mobility was measured using a Penkem 7000 instrument with varying pH of the system. ahkuseu relative mobility in soil formate tick pH10~8.5 (relative mobility acoustophoretic; RAM) was approximately -1.8 X 10 ^-10 and +1.2 X 10 ^-10 at pH 8~2. It is anionic (charged to negative) at high pH and cationic (charged to positive) at low pH, which means that tertiary amine groups are either uncharged or quantized, resulting in tertiary amine groups. It clearly shows the attachment to the particles.

Example 10

Latex polymer A has a solids content of 39.7% (2-ethhexyl acrylate 54 / styrene 2.0 / acrylonitrile 25 / methacrylic acid 4 / acetoacetoxyethyl acrylate 15) 50 // (isobutylmethacrylate 40 / methyl Methacrylate 58 / methacrylic acid 2) a two-stage emulsion polymer which is a composition of 50, and latex B is (butylacrylate 3 / styrene 91.6 / divinylbenzene 4.4 / methacrylic acid 1) 50 // with a solid content of 41.6% (Butylacrylate 83 / acetoacetoxyethylacrylate 10 / methacrylic acid 7) is a two-stage emulsion polymer that is a composition of 50, both of which are prepared by conventional methods well known in the art. The following examples are prepared by taking a latex sample (100 gr) and treating it with butyl cellosolve (8.93 gr) and butyl carbitol (2.98 gr) and then adding the appropriate amount of the following functional amines.

These examples demonstrate that diamines, where one is a primary amine and the other is a secondary amine, can be used for wood substrates as well as to improve the solvent resistance and print resistance of the clear coating to other solid substrates. will be.

Test Methods

Print resistance test

The film was cast on aluminum with 1 mil DFT and air dried for 4 hours. Cheese cloth was placed on the film and the cheese cloth was loaded to a pressure of 4 psi. After 4 hours, the load and the cheese cross were removed and the impression was made by the cheese cross. The samples were graded in 0-10 steps, with 0 indicating complete failure with irreversible attachment of the cheesecross to the coating and 10 indicating no visible damage to the coating when the cheesecross was removed.

Acetone Spot Test

A 1 mil DFT film was cast on aluminum and air dried for 1 week. Glass fiber filter discs (Gelman 66075 or the like) were immersed in acetone and placed on a film and covered with a watch plate. After 2 minutes the filter was removed, the excess acetone was sucked into the tissue and the film was examined for damage. Samples were graded in 0-10 steps, with 0 indicating complete failure by dissolving the coating in solvent and 10 indicating no visible damage to the coating.

MEK Swelling Ratio Test

A latex polymer film was cast on the polypropylene sheet to have a wet thickness of about 10-12 mils and a dry film thickness of about 2 mils. The dry film was removed from the polypropylene and cut into 1 cm x 1 cm samples. The sample was immersed in methyl ethyl ketone for two hours. The length of one edge was measured for the sample swollen from the solvent. As a result, the length was cubed and represented as a swelling value. Lower values inherently indicate superior solvent resistance of the coating.

The meaning of the terms used in the specification will be described in detail.

The Tg of the polymer is a measure of the hardness and melt flow of the polymer. The higher the Tg, the smaller and harder the melt flow of the coating. Tg is described in Principles of Polymer Chemistry (1953, Cornell University Press). Tg is measured or Bull. Amer. It can be calculated as described by FOX in Physics Soc., 1, 3, page 123 (1956).

The Tg used here is the value actually measured. A differential scanning calorimeter (DSC) can be used for measuring the Tg of the polymer (at a heating rate of 10 ° C./min, the Tg value of the first half point). ).

DFT is the dry film thickness.

Claims (15)

A method of producing a functional polymer comprising reacting an acetoacetate-functional polymer under primary enamine and a compound having at least one other form of functional group under the conditions for producing enamine. Polymerizing the monomer mixture containing the acetoacetate monomer under conditions that are not miscible with the functional group; And after the polymerization, reacting the acetoacetate-functional polymer product with the primary amine and the compound having an immiscible functional group under the effective production conditions of the enamine. The method of claim 1 or 2, wherein the functional group is a bonding group selected from the group consisting of divalent groups such as C ₂ -C ₁₈ alkyl, alkoxyl and polyalkoxyl chains having a molecular weight of about 72-400,000. The method according to claim 1 or 2, wherein the functional group is mercaptoethylamine, taurine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, polyoxypropyleneamine, polyoxyethyleneamine, 2-aminoethyl And ethyleneurea, 2-diethylaminoethylamine, amino acid, allylamine and 4-amino-2,2,6,6-tetramethylpiperidine. The method of claim 2, wherein the amount of functional amine can vary from one molar excess to one molar excess based on the amount of acetoacetate functional group. An emulsion polymer having a mercaptan functional group attached through an enamine of an acetoacetate functional group. An emulsion polymer having an alkoxy silane functional group attached through an enamine of an acetoacetate functional group. An emulsion polymer having olefin functional groups attached to the vinyl polymer via the enamine of the acetoacetate functional groups. An emulsion polymer having a secondary amine functional group attached through an enamine of an acetoacetate functional group. Coating composition using the emulsion polymer of claim 9 having print resistance and solvent resistance An emulsion polymer having an adhesion-promoting group attached through an enamine of an acetoacetate functional group. A coating composition containing the polymer of claim 6, 7, 8, 9 or 11. The method of claim 2 wherein the polymer is a water soluble emulsion polymer prepared from an insoluble emulsion polymer by adding an amine functional polyethylene oxide. The method of claim 2 wherein the polymer is characterized in that Tg is adjusted by adding functional amines. An emulsion polymer having a polyethylene oxide group attached through an enamine of an acetoacetate functional group to produce a steric stabilized latex.